US20200180967A1 - Silicon dioxide composite particle with far-infrared radioactivity; precursor of the same and application thereof - Google Patents
Silicon dioxide composite particle with far-infrared radioactivity; precursor of the same and application thereof Download PDFInfo
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- US20200180967A1 US20200180967A1 US16/531,947 US201916531947A US2020180967A1 US 20200180967 A1 US20200180967 A1 US 20200180967A1 US 201916531947 A US201916531947 A US 201916531947A US 2020180967 A1 US2020180967 A1 US 2020180967A1
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- United States
- Prior art keywords
- silicon dioxide
- dioxide composite
- precursor
- composite particles
- far
- Prior art date
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Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 69
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 69
- 239000011246 composite particle Substances 0.000 title claims abstract description 65
- 239000002243 precursor Substances 0.000 title claims abstract description 52
- 229910000077 silane Inorganic materials 0.000 claims abstract description 30
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 230000007062 hydrolysis Effects 0.000 claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000012643 polycondensation polymerization Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 230000002285 radioactive effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- QQPPECOPIWMCQI-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCCC[Si](OCC)(OCC)OCC QQPPECOPIWMCQI-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 230000005855 radiation Effects 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 230000003833 cell viability Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 6
- 0 CC.CC.CC(C)CC(=O)C1=CC=CC=C1.CC(C)N=CC1=CC=CC=C1.[3*]C(=O)CC(C)C.[3*]C(=O)CCN(CCC([3*])=O)C(C)C.[3*]C(=O)CCN([H])C(C)C.[3*]C(C)C Chemical compound CC.CC.CC(C)CC(=O)C1=CC=CC=C1.CC(C)N=CC1=CC=CC=C1.[3*]C(=O)CC(C)C.[3*]C(=O)CCN(CCC([3*])=O)C(C)C.[3*]C(=O)CCN([H])C(C)C.[3*]C(C)C 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- BYBPUTVZGSFFFS-UHFFFAOYSA-N 2-ethyl-N-(3-triethoxysilylpropyl)hexanamide Chemical compound C(C)C(C(=O)NCCC[Si](OCC)(OCC)OCC)CCCC BYBPUTVZGSFFFS-UHFFFAOYSA-N 0.000 description 4
- GHHYMGSXKFDGTR-UHFFFAOYSA-N 4-hexyl-N-(3-triethoxysilylpropyl)benzamide Chemical compound C(C)O[Si](CCCNC(C1=CC=C(C=C1)CCCCCC)=O)(OCC)OCC GHHYMGSXKFDGTR-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000003115 biocidal effect Effects 0.000 description 4
- -1 but not limited to Chemical group 0.000 description 4
- 231100000135 cytotoxicity Toxicity 0.000 description 4
- 230000003013 cytotoxicity Effects 0.000 description 4
- 231100000263 cytotoxicity test Toxicity 0.000 description 4
- MVUXVDIFQSGECB-UHFFFAOYSA-N ethyl n-(3-triethoxysilylpropyl)carbamate Chemical compound CCOC(=O)NCCC[Si](OCC)(OCC)OCC MVUXVDIFQSGECB-UHFFFAOYSA-N 0.000 description 4
- 239000007758 minimum essential medium Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 210000002966 serum Anatomy 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WTYCVSZLGLYBAR-UHFFFAOYSA-N 1-(4-octoxyphenyl)-N-(3-triethoxysilylpropyl)methanimine Chemical compound C(CCCCCCC)OC1=CC=C(C=NCCC[Si](OCC)(OCC)OCC)C=C1 WTYCVSZLGLYBAR-UHFFFAOYSA-N 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 206010022998 Irritability Diseases 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 231100000002 MTT assay Toxicity 0.000 description 2
- 238000000134 MTT assay Methods 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910007157 Si(OH)3 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000004113 cell culture Methods 0.000 description 2
- 231100000433 cytotoxic Toxicity 0.000 description 2
- 230000001472 cytotoxic effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 210000002950 fibroblast Anatomy 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- WFSGQBNCVASPMW-UHFFFAOYSA-N 2-ethylhexanoyl chloride Chemical compound CCCCC(CC)C(Cl)=O WFSGQBNCVASPMW-UHFFFAOYSA-N 0.000 description 1
- 229940082584 3-(triethoxysilyl)propylamine Drugs 0.000 description 1
- XRAHLPNMIIAEPP-UHFFFAOYSA-N 4-hexylbenzoyl chloride Chemical compound CCCCCCC1=CC=C(C(Cl)=O)C=C1 XRAHLPNMIIAEPP-UHFFFAOYSA-N 0.000 description 1
- KVOWZHASDIKNFK-UHFFFAOYSA-N 4-octoxybenzaldehyde Chemical compound CCCCCCCCOC1=CC=C(C=O)C=C1 KVOWZHASDIKNFK-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- RBSXIZJIWBWEJZ-UHFFFAOYSA-N CCCCC(CC)COC(=O)CCCCCC[Si](OCC)(OCC)OCC Chemical compound CCCCC(CC)COC(=O)CCCCCC[Si](OCC)(OCC)OCC RBSXIZJIWBWEJZ-UHFFFAOYSA-N 0.000 description 1
- UCQMTHYWUJZFQF-UHFFFAOYSA-N CCCCC(CC)COC(=O)CCN(CCC[Si](OCC)(OCC)OCC)CCC(=O)OCC(CC)CCCC Chemical compound CCCCC(CC)COC(=O)CCN(CCC[Si](OCC)(OCC)OCC)CCC(=O)OCC(CC)CCCC UCQMTHYWUJZFQF-UHFFFAOYSA-N 0.000 description 1
- JQBOLPXGPWSDPQ-UHFFFAOYSA-N CCO[Si](CCCN=CC1=CC=C(C)C=C1)(OCC)OCC Chemical compound CCO[Si](CCCN=CC1=CC=C(C)C=C1)(OCC)OCC JQBOLPXGPWSDPQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 210000003719 b-lymphocyte Anatomy 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- 238000003570 cell viability assay Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- IRUHTDGKUWERCQ-UHFFFAOYSA-N n-propyl-3-triethoxysilylpropan-1-amine Chemical compound CCCNCCC[Si](OCC)(OCC)OCC IRUHTDGKUWERCQ-UHFFFAOYSA-N 0.000 description 1
- PGSADBUBUOPOJS-UHFFFAOYSA-N neutral red Chemical compound Cl.C1=C(C)C(N)=CC2=NC3=CC(N(C)C)=CC=C3N=C21 PGSADBUBUOPOJS-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000015816 nutrient absorption Nutrition 0.000 description 1
- 235000021062 nutrient metabolism Nutrition 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/126—Preparation of silica of undetermined type
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/88—Isotope composition differing from the natural occurrence
Definitions
- the present disclosure relates to a silicon dioxide composite particle and in particular to a silicon dioxide composite particle with far-infrared radiation and low biotoxicity, which renders its extensive use in biological products.
- Far-infrared radiation refers to radiation with wavelengths ranging from 4.0 ⁇ m and 1000 ⁇ m, which is in the non-visible spectrum. Specifically, radiation with wavelengths between 4 and 14 ⁇ m affects the physical or chemical properties of organisms; it is closely related to the growth of organisms and is also known as the light of life.
- the far-infrared materials mainly absorb thermal energy in the environment and then convert the thermal energy into far-infrared radiation.
- Most of the conventional far-infrared materials are inorganic nano materials, such as oxides, carbides, borides, silicides or nitrides.
- all of the above materials are natural or man-made minerals or compounds with a particular percentage of metal.
- These materials are further processed by high-temperature sintering and then ground to far-infrared nanoparticles having good far-infrared radiation.
- the far-infrared radiation compound since the far-infrared radiation compound is a nano-sized particle, it may enter the living body through respiration and the trace amounts of heavy metal may cause damage to the organism. Thus, the application thereof is inherently limited.
- the inorganic nano materials may cause allergic reactions or irritations when in direct contact with human skin.
- the present disclosure provides an organic silane precursor.
- the organic precursor undergoes a polycondensation reaction with tetra-alkoxysilane, the precursor bonds to the hydroxyl group exposed on the surface of the silicon dioxide particles, thereby forming a long carbon-chain structure which comes in direct contact with the skin and reduces the irritability caused by the hydroxyl group.
- the organic precursor provided by the present disclosure is comprised of a long carbon-chain structure which generates a steric barrier to reduce the mutual polymerization between the organic precursors. Accordingly, the organic precursor is highly stable.
- one of the aspects of the present disclosure is to provide an organic silane precursor in the preparation of a silicon dioxide composite particle, wherein the organic precursor is of the formula (I) A-R 1 -Si(OR 2 ) 3 , wherein R 1 is a C 2-4 alkylene group, R 2 is a C 1-2 alkyl group, A is selected from
- R 3 is selected from an unsubstituted C 1-18 linear or branched alkyl group or alkoxyl group, and n is 1 to 5.
- R 4 is selected from an unsubstituted C 1-18 linear or branched alkyl group.
- a further aspect of the present disclosure relates to a method for using the precursor of the above formula (I) to prepare a silicon dioxide composite particle.
- the method involves the following steps: mixing the organic silane precursor and tetra-alkoxy silane in an alcohol solvent to form a mixture; adding an alkaline solution to the mixture to undergo hydrolysis and condensation polymerization, and obtaining another mixture with solids; filtering, washing and drying the solid particles to obtain the silicon dioxide composite particles.
- the tetra-alkoxy silane is tetra ethoxysilane.
- the alcohol solvent is ethanol solution.
- the alkaline solution is ammonia solution.
- a further aspect of the present disclosure relates to silicon dioxide composite particles with far-infrared radioactivity, which is prepared from the above method for preparing the silicon dioxide composite particles.
- the sole FIGURE is a flow chart showing the method for preparing the silicon dioxide composite particles according to one of the embodiments of the present disclosure.
- precursor means a precursor compound that undergoes a particular chemical reaction, causing a change in the chemical structure, to obtain a particular physical property or chemical property, wherein the chemical reaction includes hydrolysis, polymerization or condensation.
- alkyl group means a linear chain, branched chain or saturated aliphatic group having 1 to about 18 carbons.
- the alkyl group may include any number of the carbon atoms, and the number of carbon atoms may be further defined.
- C 1-2 means an alkyl group having 1 or 2 carbon atoms.
- C 1-3 means an alkyl group having 1 to 3 carbon atoms.
- C 1-4 means an alkyl group having 1 to 4 carbon atoms.
- C 2-4 means an alkyl group having 2 to 4 carbon atoms.
- the C 1-6 alkyl group includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, etc.
- the alkyl group can also refer to an alkyl group having up to 18 carbon atoms including, but not limited to, heptyl, octyl, nonyl, decyl, etc.
- alcohol means an organic compound having a hydroxyl group (—OH) bonded to a carbon atom.
- —OH hydroxyl group
- alkaline solution means a solution with a pH value of more than 7 or the concentration of hydroxide ions is higher than the concentration of hydrogen ions at room temperature.
- composite particle means a functional substance, prepared by hydrolysis, condensation, polymerization, or any chemical reaction of a specific precursor and a particular metal/metalloid/nonmetal particle, and also any product directly or indirectly obtained from the composite particle.
- the organic precursor for preparing the silicon dioxide composite particles is the organic precursor for preparing the silicon dioxide composite particles.
- the present disclosure provides a compound for the formula (I):
- A-R 1 —Si(OR 2 ) 3 wherein R 1 is C 2-4 alkylene group, R 2 is C 1-2 alkyl group, A is selected from
- R 3 is selected from an unsubstituted C 1-18 linear or branched alkyl group or alkoxyl group, and the number of the group can be 1, 2, 3, 4 or 5.
- the linear alkyl group can be, for example, methyl, ethyl, propyl, butyl, pentyl or hexyl.
- the branched alkyl group can be, for example, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl.
- the alkoxyl group can be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, 2-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy or hexyloxy, etc.
- R 3 may be an unsubstituted C 1-18 linear or branched alkyl or alkoxyl group, which effectively provides a steric barrier to prevent the A-R 1 —Si(OR 2 ) 3 from intermolecular self-polymerization to form nano-particles. Consequently, there is greater stability of the organic silane precursor.
- a further aspect of the present disclosure provides a method for preparing silicon dioxide composite particles.
- the method consists of the following steps:
- step S 10 the organic silane precursor and tetra-alkox silane were added to the alcohol solvent to form a mixture.
- the properties of the organic silane precursor are as described above.
- the tetra-alkox silane may be, for example, tetra ethoxysilane, but is not limited thereto.
- the alcohol solvent may be, but is not limited to, an ethanol solution.
- the alkaline solution is added to the mixture obtained from step S 10 to undergo hydrolysis and condensation polymerization.
- the alkaline solution may be an ammonia solution, but is not limited thereto.
- the tetra-alkox silane forms a silicon dioxide material, and the —Si(OR 2 ) 3 in the organic precursor structure is hydrolyzed to —Si(OH) 3 .
- the organic silane precursor and the silicon dioxide material undergo condensation and polymerization between the —Si(OH) 3 of the organic precursor and the hydroxyl group on the surface of the silicon dioxide material, so that the hydroxyl group on the surface of the silicon dioxide particles is replaced by the groups of the organic precursor.
- steps S 14 and S 16 another mixture containing solids obtained from step S 12 is filtered, washed and dried to obtain the silicon dioxide composite particles.
- the methods for filtration, washing, and drying are well known in the art and are thus not described herein.
- the present disclosure provides a method to prepare silicon dioxide composite particles with far-infrared radioactivity.
- the silicon dioxide composite particles with lower biological toxicity are due to the organic silane precursor of the present disclosure. Accordingly, the silicon dioxide composite particles can be applicable to the products that are used as far-infrared treatments or cures.
- a single neck reaction flask with 100 mL volume was provided. 10 mL of dry dichloromethane and 2.22 g of (N-(3-(triethoxysilyl)propyl)propylamine (10 mmol) were added to the single neck reaction flask to give an initial solution, which was placed in an ice-water bath at 0° C. Next, 2.20 g of dodecanoyl chloride (10 mmol) was slowly dropped into the initial solution. After 20 minutes of reaction time, 1.12 g of triethylamine (11 mmol) was slowly added to obtain a mixture.
- Embodiment 1 The dodecanoyl chloride in Embodiment 1 was replaced by 2-ethyl hexanoyl chloride, and the other steps were the same as those in Embodiment 1. After the reaction was complete, 2-ethyl-N-(3-(triethoxysilyl)propyl)hexanamide (2.85 g, 8.2 mmol) was obtained.
- Embodiment 1 The dodecanoyl chloride in Embodiment 1 was replaced by 4-hexyl-benzoylchloride, and the other steps were the same as those in Embodiment 1. After the reaction was complete, N-(3-(triethoxysilyl)propyl)-4-hexylbenzamide (3.56 g, 8.7 mmol) was obtained.
- Embodiment 1 The dodecanoyl chloride in Embodiment 1 was replaced by ethyl chloroformate, and the other steps were the same as those in Embodiment 1, and thus will not be described herein. After the reaction was complete, ethyl(3-(triethoxysilyl)propyl)carbamate (2.32 g, 7.9 mmol) was obtained.
- Embodiment 1 The dodecanoyl chloride in Embodiment 1 was replaced by 2-ethylhexyl acrylate, and the other steps were the same as those in Embodiment 1. After the reaction was complete, N-(2-ethylhexyl) propanoate-3-(triethoxysilyl) propyl-1-amine (2.96 g, 7.3 mmol) was obtained.
- Embodiment 1 The dodecanoyl chloride (10 mmol) in Embodiment 1 was replaced by 2-ethylhexyl acrylate (20 mmol), and the other steps were the same as those in Embodiment 1. After the reaction was complete, N-Di ((2-ethylhexyl)propanoate)-3-(triethoxysilyl)propyl-1-amine (4.60 g, 7.8 mmol) was obtained.
- a single neck reaction flask with 50 mL volume was provided. 2.22 g of 3-(triethoxysilyl)propylamine (10 mmol), 2.34 g of 4-octyloxy benzaldehyde (10 mmol), and 10 mL of toluene solution were added into the single neck reaction flask to obtain a mixture. After 5 hours of reaction time at a temperature of 40° C., the toluene solution was removed with a rotary evaporator to obtain N-(4-(octyloxy)benzylidene)-3-(triethoxysilyl)propan-1-amine (3.20 g, 9.2 mmol).
- the N-(3-(triethoxysilyl)propyl)dodecanamide from Embodiment 1 was replaced by commercially available N-propyltriethoxysilane, and 6.2 g of silicon dioxide composite particles were obtained; the yield was 95.2%.
- the N-(3-(triethoxysilyl)propyl)dodecanamide from Embodiment 1 was replaced by commercially available N-octyltriethoxysilane, and 6.6 g of silicon dioxide composite particles were obtained; the yield was 96.1%.
- the test samples were measured using a far-infrared emissivity analyzer (label: Japan Sensor Corporation; model: TSS-5X). The measurement conditions are described below.
- the measurement temperature was 25° C.
- the measurement wavelength range was between 2 ⁇ m and 22 ⁇ m.
- the far-infrared emissivity of the silicon dioxide composite particles from Embodiments 8 to 16 was greater than 90%. Further, each silicon dioxide composite particle prepared from the precursors from Embodiments 1-7 of the present disclosure, respectively, had a far-infrared emissivity equivalent to, or even better than the far-infrared emissivity of the silicon dioxide composite particles prepared from a commercially available precursor. Accordingly, the precursors from Embodiments 1-7 can indeed provide silicon dioxide composite particles with far-infrared radioactivity.
- This embodiment is a cytotoxicity test using the Agar Diffusion Method.
- Mouse fibroblast cells (L929, CCRC 60091 NCTN Clone 929, of strain L) were implanted into each well of a 6-well plate and a minimum essential medium (MEM) containing 10% serum and 1% antibiotic was added to each well for cell culture. After the cells grew a sub-confluent monolayer, 2 mL of 1.5% agar was added. After the agar solidified, the test sample of the silicon dioxide composite particles was added to one of the wells, and no other sample of the composite particles was added to the remaining wells to act as a control group. Next, the 6-well plate was placed in an incubator with 5% carbon dioxide at 37° C.
- 0.2 g of the product from Embodiment 8 was mixed with a minimum essential medium containing 10% serum and 1% antibiotic to form a solution with a 0.2 g/mL concentration.
- the reaction index of the testing sample from Embodiment 8 was 0/0.
- the reaction index of the testing sample from Embodiment 16 was 0/0.
- the reaction index of the testing sample from Comparative Example 1 was 5/5.
- This embodiment is a cytotoxicity test using MTT assay.
- Mouse fibroblast cells (CCRC 60091 NCTN Clone 929, of strain L) were implanted into each well of a 96-well plate and a minimum essential medium (MEM) containing 10% serum and 1% antibiotic was added to each well for cell culture. After the cells grew to a sub-confluent monolayer, 0.1 mL of test sample was added into part of the wells, and no other sample of the composite particles was added to the remaining wells do to act as a control group. Next, the 96-well plate was placed in an incubator with 5% carbon dioxide at 37° C. for 24 hours, and then MTT assay was conducted to analyze cell viability.
- MEM minimum essential medium
- the product from Embodiment 8 will be used as an example to explain the preparation process.
- the product from Embodiment 16 and the product from Comparative Example 1 were also prepared for testing by the same process.
- 0.2 g of the product from Embodiment 8 was mixed with a minimum essential medium containing 10% serum and 1% antibiotic to form a solution with a 0.2 g/mL concentration.
- the cell viability of the testing sample from Embodiment 8 was 80.4 ⁇ 10.2%.
- the cell viability of the testing sample from Embodiment 16 was 99.4 ⁇ 8.6%.
- the cell viability of the testing sample from Comparative Example 1 was 35.4 ⁇ 4.9%.
- Embodiments 18-19 are shown in Table 2.
- the cell viability assays were 80.4 ⁇ 10.2% and 99.4 ⁇ 8.6%, respectively. These results show that the sample was not cytotoxic. Accordingly, the silicon dioxide composite particles prepared from the precursor disclosed in the present disclosure does indeed have very low biotoxicity, which makes it of great potential for extensive use in organisms.
- the organic silane precursor disclosed in the present disclosure can reduce the toxicity of silicon dioxide composite particles to organisms. Further, the long carbon chain of the organic silane precursor provides a steric barrier, which can prevent the alkoxysilane of the organic silane precursor from self-polymerization to form nano-particles and improve stability. Accordingly, the present disclosure provides the organic silane precursor, the method for preparing the silicon dioxide composite particles by using the organic silane precursor, and the silicon dioxide composite particles prepared from the organic silane precursor to solve the problems of conventional techniques and increase the applicability of the silicon dioxide composite particles.
Abstract
A-R1—Si(OR2)3 Formula (I)
Description
- The present disclosure relates to a silicon dioxide composite particle and in particular to a silicon dioxide composite particle with far-infrared radiation and low biotoxicity, which renders its extensive use in biological products.
- Far-infrared radiation refers to radiation with wavelengths ranging from 4.0 μm and 1000 μm, which is in the non-visible spectrum. Specifically, radiation with wavelengths between 4 and 14 μm affects the physical or chemical properties of organisms; it is closely related to the growth of organisms and is also known as the light of life.
- For example, there are many functional groups in human cells that can absorb the energy of far-infrared radiation with wavelengths between 4 and 14 μm, such as the hydroxyl and carbonyl groups. The absorption wavelength for water molecules is about 6.27 μm, and after absorbing the radiation, the water molecule will rotate, which breaks the hydrogen bonds between water molecules so that the water-clusters turn into individual water molecules. The individual water molecules can easily enter the cells to promote further intracellular biochemical reactions, accelerate blood circulation and improve nutrient absorption and metabolism. Therefore, many far-infrared materials have been developed for these purposes.
- The far-infrared materials mainly absorb thermal energy in the environment and then convert the thermal energy into far-infrared radiation. Most of the conventional far-infrared materials are inorganic nano materials, such as oxides, carbides, borides, silicides or nitrides. However, all of the above materials are natural or man-made minerals or compounds with a particular percentage of metal. These materials are further processed by high-temperature sintering and then ground to far-infrared nanoparticles having good far-infrared radiation. Nevertheless, since the far-infrared radiation compound is a nano-sized particle, it may enter the living body through respiration and the trace amounts of heavy metal may cause damage to the organism. Thus, the application thereof is inherently limited. In addition, the inorganic nano materials may cause allergic reactions or irritations when in direct contact with human skin.
- In view of the above-mentioned issues of the conventional far-infrared materials, it is necessary to improve the properties of the far-infrared materials to boost their market potential and wider applicability.
- The present disclosure provides an organic silane precursor. When the organic precursor undergoes a polycondensation reaction with tetra-alkoxysilane, the precursor bonds to the hydroxyl group exposed on the surface of the silicon dioxide particles, thereby forming a long carbon-chain structure which comes in direct contact with the skin and reduces the irritability caused by the hydroxyl group.
- In addition, the organic precursor provided by the present disclosure is comprised of a long carbon-chain structure which generates a steric barrier to reduce the mutual polymerization between the organic precursors. Accordingly, the organic precursor is highly stable.
- Therefore, one of the aspects of the present disclosure is to provide an organic silane precursor in the preparation of a silicon dioxide composite particle, wherein the organic precursor is of the formula (I) A-R1-Si(OR2)3, wherein R1 is a C2-4 alkylene group, R2 is a C1-2 alkyl group, A is selected from
- R3 is selected from an unsubstituted C1-18 linear or branched alkyl group or alkoxyl group, and n is 1 to 5.
- According to some implementations of the present disclosure, the alkoxyl group is
- wherein R4 is selected from an unsubstituted C1-18 linear or branched alkyl group.
- A further aspect of the present disclosure relates to a method for using the precursor of the above formula (I) to prepare a silicon dioxide composite particle. The method involves the following steps: mixing the organic silane precursor and tetra-alkoxy silane in an alcohol solvent to form a mixture; adding an alkaline solution to the mixture to undergo hydrolysis and condensation polymerization, and obtaining another mixture with solids; filtering, washing and drying the solid particles to obtain the silicon dioxide composite particles.
- According to some embodiments of the present disclosure, the tetra-alkoxy silane is tetra ethoxysilane.
- According to some embodiments of the present disclosure, the alcohol solvent is ethanol solution.
- According to some embodiments of the present disclosure, the alkaline solution is ammonia solution.
- A further aspect of the present disclosure relates to silicon dioxide composite particles with far-infrared radioactivity, which is prepared from the above method for preparing the silicon dioxide composite particles.
- The sole FIGURE is a flow chart showing the method for preparing the silicon dioxide composite particles according to one of the embodiments of the present disclosure.
- In the present disclosure, the term “precursor” means a precursor compound that undergoes a particular chemical reaction, causing a change in the chemical structure, to obtain a particular physical property or chemical property, wherein the chemical reaction includes hydrolysis, polymerization or condensation.
- In the present disclosure, the term “alkyl group” means a linear chain, branched chain or saturated aliphatic group having 1 to about 18 carbons. The alkyl group may include any number of the carbon atoms, and the number of carbon atoms may be further defined. For example, C1-2 means an alkyl group having 1 or 2 carbon atoms. C1-3 means an alkyl group having 1 to 3 carbon atoms. C1-4 means an alkyl group having 1 to 4 carbon atoms. C2-4 means an alkyl group having 2 to 4 carbon atoms. For example, the C1-6 alkyl group includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, etc. The alkyl group can also refer to an alkyl group having up to 18 carbon atoms including, but not limited to, heptyl, octyl, nonyl, decyl, etc.
- In the present disclosure, the term “alcohol” means an organic compound having a hydroxyl group (—OH) bonded to a carbon atom. For example, methanol, propanol, isopropanol, butanol, octanol, isooctyl alcohol, ethylene glycol, etc.
- In the present disclosure, the term “alkaline solution” means a solution with a pH value of more than 7 or the concentration of hydroxide ions is higher than the concentration of hydrogen ions at room temperature. For example, sodium hydroxide solution, potassium hydroxide solution, sodium hydrogencarbonate solution, potassium hydrogencarbonate solution, sodium carbonate solution, potassium carbonate solution, triethylamine, pyridine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, 3-methylpyridine, or 2,4,6-trimethylpyridine, etc.
- In the present disclosure, the term “composite particle” means a functional substance, prepared by hydrolysis, condensation, polymerization, or any chemical reaction of a specific precursor and a particular metal/metalloid/nonmetal particle, and also any product directly or indirectly obtained from the composite particle.
- In view of the problems with the conventional silicon dioxide composite particles, including uneven particle size distribution, biotoxicity and allergenicity, the present disclosure proposes solutions for such technical problems. The features of the present disclosure and the achieved efficacy will be explained in detail with reference to the detailed description and preferred embodiments.
- The organic precursor for preparing the silicon dioxide composite particles.
- In one embodiment, the present disclosure provides a compound for the formula (I):
- A-R1—Si(OR2)3, wherein R1 is C2-4 alkylene group, R2 is C1-2 alkyl group, A is selected from
- R3 is selected from an unsubstituted C1-18 linear or branched alkyl group or alkoxyl group, and the number of the group can be 1, 2, 3, 4 or 5. The linear alkyl group can be, for example, methyl, ethyl, propyl, butyl, pentyl or hexyl. The branched alkyl group can be, for example, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl. The alkoxyl group can be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, 2-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy or hexyloxy, etc.
- When silicon dioxide composite particles are obtained from the organic precursor and the silicon dioxide particles by a polycondensation reaction, A-R1—Si(OR2)3 bonds to a hydroxyl group exposed on the surface of the silicon dioxide particles, thereby reducing the irritability caused by the hydroxyl group and reducing the biological toxicity of the silicon dioxide composite particles to the organisms, so that the applicability of the silicon dioxide composite particles can be increased.
- Further, in the structure of the organic silane precursor, R3 may be an unsubstituted C1-18 linear or branched alkyl or alkoxyl group, which effectively provides a steric barrier to prevent the A-R1—Si(OR2)3 from intermolecular self-polymerization to form nano-particles. Consequently, there is greater stability of the organic silane precursor.
- Preparation of the Silicon Dioxide Composite Particles
- A further aspect of the present disclosure provides a method for preparing silicon dioxide composite particles. The method consists of the following steps:
-
- Step S10: mixing the organic silane precursor and the tetra-alkox silane in an alcohol solvent to form a mixture;
- Step S12: adding an alkaline solution to the mixture to undergo hydrolysis and condensation polymerization, and obtaining another mixture containing solids;
- Step S14: filtering the solid particles; and
- Step S16: washing and drying the solid particles to obtain the silicon dioxide composite particles.
- In the method, as shown in step S10, the organic silane precursor and tetra-alkox silane were added to the alcohol solvent to form a mixture. The properties of the organic silane precursor are as described above. The tetra-alkox silane may be, for example, tetra ethoxysilane, but is not limited thereto. The alcohol solvent may be, but is not limited to, an ethanol solution.
- Next, as shown in step S12, the alkaline solution is added to the mixture obtained from step S10 to undergo hydrolysis and condensation polymerization. The alkaline solution may be an ammonia solution, but is not limited thereto. In this step, the tetra-alkox silane forms a silicon dioxide material, and the —Si(OR2)3 in the organic precursor structure is hydrolyzed to —Si(OH)3. The organic silane precursor and the silicon dioxide material undergo condensation and polymerization between the —Si(OH)3 of the organic precursor and the hydroxyl group on the surface of the silicon dioxide material, so that the hydroxyl group on the surface of the silicon dioxide particles is replaced by the groups of the organic precursor.
- Further, as shown in steps S14 and S16, another mixture containing solids obtained from step S12 is filtered, washed and dried to obtain the silicon dioxide composite particles. In these two steps, the methods for filtration, washing, and drying are well known in the art and are thus not described herein.
- Silicon Dioxide Composite Particles with Far-Infrared Radioactivity
- In another aspect, the present disclosure provides a method to prepare silicon dioxide composite particles with far-infrared radioactivity. The silicon dioxide composite particles with lower biological toxicity are due to the organic silane precursor of the present disclosure. Accordingly, the silicon dioxide composite particles can be applicable to the products that are used as far-infrared treatments or cures.
- The following embodiments are given by way of illustration to help those skilled in the art to fully understand the spirit of the present application. Hence, it should be noted that the present application is not limited to the embodiments herein and can be realized by various forms.
-
- A single neck reaction flask with 100 mL volume was provided. 10 mL of dry dichloromethane and 2.22 g of (N-(3-(triethoxysilyl)propyl)propylamine (10 mmol) were added to the single neck reaction flask to give an initial solution, which was placed in an ice-water bath at 0° C. Next, 2.20 g of dodecanoyl chloride (10 mmol) was slowly dropped into the initial solution. After 20 minutes of reaction time, 1.12 g of triethylamine (11 mmol) was slowly added to obtain a mixture. After 2 hours of reaction time, the mixture was poured into a 250 mL extraction flask, and then washed twice with 30 mL of a 0.5 M sodium hydroxide solution, and further washed once with 50 mL of water to obtain an organic layer solution. The organic layer solution was added to anhydrous magnesium sulfate and then filtered. After removing the organic solvent with a rotary evaporator (PAMCHUM SCIENTIFIC CORP., R-2000S-B1), N-(3-(triethoxysilyl)propyl) dodecanamide (3.55 g, 8.8 mmol) was obtained.
- 1H NMR (300 MHz, CDCl3), δ(ppm): 0.59 (t, J=7.8 Hz, 2H, CH2—Si), 0.83 (t, J=6.9 Hz, 3H, 1×CH3), 1.18 (t, J=7.2 Hz, 9H, 3×CH3—COSi), 1.21 (s, 16H, 8×CH2), 1.5˜31.63 (m, 4H, 1×CH2+1×CH2—CSi), 2.11 (t, J=7.8 Hz, 2H, 1×CH2—C═O), 3.20 (q, J=6.0 Hz, 2H, 1×CH2—N), 3.78 (q, J=6.9 Hz, 6H, 3×CH2—OSi), 5.84 (s, 1H, 1×NH). MS: m/z 404.3 (M+H)+.
-
- The dodecanoyl chloride in Embodiment 1 was replaced by 2-ethyl hexanoyl chloride, and the other steps were the same as those in Embodiment 1. After the reaction was complete, 2-ethyl-N-(3-(triethoxysilyl)propyl)hexanamide (2.85 g, 8.2 mmol) was obtained.
- 1H NMR (300 MHz, CDCl3), δ(ppm): 0.60 (t, J=7.8 Hz, 2H, CH2—Si), 0.84 (t, J=6.9 Hz, 6H, 2×CH3), 1.12˜1.48 (m, 13H, 3×CH3—COSi+2×CH2), 1.53˜1.64 (m, 4H, 2×CH2), 1.81-1.90 (m, 1H, 1×CH), 3.23 (q, J=6.6 Hz, 2H, 1×CH2—N), 3.78 (q, J=6.9 Hz, 6H, 3×CH2—OSi), 5.79 (s, 1H, 1×NH). MS: m/z 348.3 (M+H)+.
-
- The dodecanoyl chloride in Embodiment 1 was replaced by 4-hexyl-benzoylchloride, and the other steps were the same as those in Embodiment 1. After the reaction was complete, N-(3-(triethoxysilyl)propyl)-4-hexylbenzamide (3.56 g, 8.7 mmol) was obtained.
- 1H NMR (300 MHz, CDCl3), δ(ppm): 0.70 (t, J=7.8 Hz, 2H, CH2—Si), 0.87 (t, J=6.6 Hz, 3H, 1×CH3), 1.15˜1.47 (m, 15H, 3×CH3—COSi+3×CH2), 1.52˜1.81 (m, 4H, 2×CH2), 2.63 (t, J=7.5 Hz, 2H, 1×CH2), 3.45 (q, J=6.6 Hz, 2H, 1×CH2—N), 3.82 (q, J=6.9 Hz, 6H, 3×CH2—OSi), 7.22 (d, J=8.1 Hz, 2H, Ar—H), 7.67-7.81 (br, 3H, Ar—H+1×NH). MS: m/z 410.6 (M+H)+.
-
- The dodecanoyl chloride in Embodiment 1 was replaced by ethyl chloroformate, and the other steps were the same as those in Embodiment 1, and thus will not be described herein. After the reaction was complete, ethyl(3-(triethoxysilyl)propyl)carbamate (2.32 g, 7.9 mmol) was obtained.
- 1H NMR (300 MHz, CDCl3), δ(ppm): 0.50 (t, J=8.1 Hz, 2H, 1×CH2—Si), 1.10 (t, J=6.9 Hz, 12H, 3×CH3—COSi+1×CH3), 1.44˜1.54 (m, 2H, 1×CH2—CSi), 3.03 (q, J=6.6 Hz, 2H, 1×CH2—N), 3.69 (q, J=6.9 Hz, 6H, 3×CH2—OSi), 3.97 (q, J=6.9 Hz, 2H, 1×CH2—OC═O), 5.09 (s, 1H, 1×NH). MS: m/z 294.0 (M+H)+.
-
- The dodecanoyl chloride in Embodiment 1 was replaced by 2-ethylhexyl acrylate, and the other steps were the same as those in Embodiment 1. After the reaction was complete, N-(2-ethylhexyl) propanoate-3-(triethoxysilyl) propyl-1-amine (2.96 g, 7.3 mmol) was obtained.
- 1H NMR (300 MHz, CDCl3), δ(ppm): 0.58 (t, J=8.4 Hz, 2H, 1×CH2—Si), 0.78˜0.90 (br, 6H, 2×CH3), 1.17 (t, J=7.2 Hz, 9H, 3×CH3—CSi), 1.21˜1.39 (br, 8H, 4×CH2), 1.42-1.61 (m, 3H, 1×CH2+1×CH), 2.46 (t, J=6.3 Hz, 2H, 1×CH2), 2.56 (t, J=7.2 Hz, 2H, 1×CH2), 2.84 (t, J=6.6 Hz, 2H, 1×CH2), 3.76 (q, J=6.9 Hz, 6H, 3×CH2—OSi), 3.91-4.07 (m, 2H, 1×CH2). MS: m/z 406.3 (M+H)+.
-
- The dodecanoyl chloride (10 mmol) in Embodiment 1 was replaced by 2-ethylhexyl acrylate (20 mmol), and the other steps were the same as those in Embodiment 1. After the reaction was complete, N-Di ((2-ethylhexyl)propanoate)-3-(triethoxysilyl)propyl-1-amine (4.60 g, 7.8 mmol) was obtained.
- 1H NMR (300 MHz, CDCl3), δ(ppm): 0.61 (t, J=8.4 Hz, 2H, 1×CH2—Si), 0.81˜0.91 (br, 12H, 4×CH3), 1.20 (t, J=7.2 Hz, 9H, 3×CH3—CSi), 1.21˜1.41 (br, 16H, 8×CH2), 1.46-1.64 (m, 4H, 1×CH2+2×CH), 2.49 (t, J=6.3 Hz, 4H, 2×CH2), 2.59 (t, J=7.2 Hz, 2H, 1×CH2), 2.85 (t, J=6.6 Hz, 4H, 2×CH2), 3.79 (q, J=6.9 Hz, 6H, 3×CH2—OSi), 3.92-4.09 (m, 4H, 2×CH2). MS: m/z 590.4 (M+H)+.
-
- A single neck reaction flask with 50 mL volume was provided. 2.22 g of 3-(triethoxysilyl)propylamine (10 mmol), 2.34 g of 4-octyloxy benzaldehyde (10 mmol), and 10 mL of toluene solution were added into the single neck reaction flask to obtain a mixture. After 5 hours of reaction time at a temperature of 40° C., the toluene solution was removed with a rotary evaporator to obtain N-(4-(octyloxy)benzylidene)-3-(triethoxysilyl)propan-1-amine (3.20 g, 9.2 mmol).
- 1H NMR (300 MHz, CDCl3), δ(ppm): 0.66 (t, J=8.4 Hz, 2H, 1×CH2—Si), 0.87 (t, J=6.6 Hz, 3H, 1×CH3), 1.21 (t, J=6.9 Hz, 9H, 3×CH3—COSi), 1.25˜1.52 (m, 10H, 5×CH2) 1.71-1.85 (m, 4H, 2×CH2), 3.54 (t, J=6.9 Hz, 2H, 1×CH2—N), 3.81 (q, J=6.9 Hz, 6H, 3×CH2—OSi), 3.95 (t, J=6.6 Hz, 2H, 1×CH2—O), 6.88 (d, J=8.7 Hz, 2H, Ar—H), 7.63 (d, J=8.7 Hz, 2H, Ar—H), 8.17 (s, 1H, 1×CH). MS: m/z 348.3 (M+H)+.
- 2.0 g (5 mmol) of (N-(3-(triethoxysilyl)propyl)dodecanamide from Embodiment 1, 20.8 g (100 mmol) of tetraethoxysilane and 20 mL of ethanol were stirred uniformly for 3 minutes. Next, 22 mL of a 35% ammonia solution was slowly added. After 24 hours of reaction time, the filtration processed a solid. The solid was washed twice with hot water and then dried to provide 6.4 g of silicon dioxide composite particles with a yield of 85.2%.
- The N-(3-(triethoxysilyl)propyl)dodecanamide from Embodiment 1 was replaced by 2-ethyl-N-(3-(triethoxysilyl)propyl)hexanamide from Embodiment 2, and 6.3 g of silicon dioxide composite particles were obtained; the yield of the product was 85.2%. The other steps were the same as those in Embodiment 8.
- The N-(3-(triethoxysilyl)propyl)dodecanamide from Embodiment 1 was replaced by N-(3-(triethoxysilyl)propyl)-4-hexylbenzamide from Embodiment 3, and 5.65 g of silicon dioxide composite particles were obtained; the yield was 71.4%. The other steps were the same as those in Embodiment 8.
- The N-(3-(triethoxysilyl)propyl)dodecanamide from Embodiment 1 was replaced by ethyl(3-(triethoxysilyl)propyl)carbamate from Embodiment 4, and 5.25 g of silicon dioxide composite particles were obtained; the yield was 75.6%. The other steps were the same as those in Embodiment 8.
- The N-(3-(triethoxysilyl)propyl)dodecanamide from Embodiment 1 was replaced by N-(2-ethylhexyl)propanoate-3-(triethoxysilyl)propyl-1-amine from Embodiment 5, and 6.1 g of silicon dioxide composite particles were obtained; the yield was 81.1%. The other steps were the same as those in Embodiment 8.
- The N-(3-(triethoxysilyl)propyl)dodecanamide from Embodiment 1 was replaced by N-Di((2-ethylhexyl)propanoate)-3-(triethoxysilyl)propyl-1-amine from Embodiment 6, and 6.7 g of silicon dioxide composite particles were obtained; the yield was 79.4%. The other steps were the same as those in Embodiment 8.
- The N-(3-(triethoxysilyl)propyl)dodecanamide from Embodiment 1 was replaced by N-(4-(octyloxy)benzylidene)-3-(triethoxysilyl)propan-1-amine from Embodiment 7, and 6.3 g of silicon dioxide composite particle were obtained; the yield was 82.3%. The other steps were the same as those in Embodiment 8.
- The N-(3-(triethoxysilyl)propyl)dodecanamide from Embodiment 1 was replaced by commercially available N-propyltriethoxysilane, and 6.2 g of silicon dioxide composite particles were obtained; the yield was 95.2%.
- The N-(3-(triethoxysilyl)propyl)dodecanamide from Embodiment 1 was replaced by commercially available N-octyltriethoxysilane, and 6.6 g of silicon dioxide composite particles were obtained; the yield was 96.1%.
- 20.8 g (100 mmol) of tetraethoxysilane and 30 mL of ethanol were uniformly stirred for 3 minutes. Next, 22 mL of a 35% ammonia solution was slowly added. After 24 hours of reaction time, filtration was carried out to process a solid. The solid was washed twice with hot water, and then dried; 5.1 g of silicon dioxide particles were obtained, with a yield of 84.9%.
- Each of the silicon dioxide composite particles from Examples 8 to 16, respectively, was prepared on a 15×15 mm sheet-like sample for testing. The test samples were measured using a far-infrared emissivity analyzer (label: Japan Sensor Corporation; model: TSS-5X). The measurement conditions are described below. The measurement temperature was 25° C. The measurement wavelength range was between 2 μm and 22 μm.
- As shown in Table 1, the far-infrared emissivity of the silicon dioxide composite particles from Embodiments 8 to 16 was greater than 90%. Further, each silicon dioxide composite particle prepared from the precursors from Embodiments 1-7 of the present disclosure, respectively, had a far-infrared emissivity equivalent to, or even better than the far-infrared emissivity of the silicon dioxide composite particles prepared from a commercially available precursor. Accordingly, the precursors from Embodiments 1-7 can indeed provide silicon dioxide composite particles with far-infrared radioactivity.
-
TABLE 1 Embodi- Embodi- Embodi- Embodi- Embodi- ment 8 ment 9 ment 10ment 11 ment 12far-infrared 93% 94% 98% 95% 98% emissivity Compar- Embodi- Embodi- Embodi- Embodi- ative ment 13 ment 14ment 15 ment 16 example 1 far-infrared 97% 91% 93% 94% 95% emissivity - Cytotoxicity Test A
- This embodiment is a cytotoxicity test using the Agar Diffusion Method. Mouse fibroblast cells (L929, CCRC 60091 NCTN Clone 929, of strain L) were implanted into each well of a 6-well plate and a minimum essential medium (MEM) containing 10% serum and 1% antibiotic was added to each well for cell culture. After the cells grew a sub-confluent monolayer, 2 mL of 1.5% agar was added. After the agar solidified, the test sample of the silicon dioxide composite particles was added to one of the wells, and no other sample of the composite particles was added to the remaining wells to act as a control group. Next, the 6-well plate was placed in an incubator with 5% carbon dioxide at 37° C. for 24 hours, then stained with Neutral Red and then the number of viable cells was counted. One sample was investigated 3 times in total, and the qualitative results were determined according to ISO10993-5 and ASTM F895-11. The individual results of the three tests were recorded and the average value of these results was taken as the qualitative score. The Response Index (RI) is obtained based on the ratio of cell death and cell deformation. The lower the RI value is, the lower the cytotoxicity. The test result in which R.I.>1/1 means that the sample is cytotoxic. In order to describe the process of the investigation clearly, the product from Embodiment 8 will be used as an example. The product from Embodiment 16 and the product from Comparative Example 1 were also prepared for testing by the same process. 0.2 g of the product from Embodiment 8 was mixed with a minimum essential medium containing 10% serum and 1% antibiotic to form a solution with a 0.2 g/mL concentration. The reaction index of the testing sample from Embodiment 8 was 0/0. The reaction index of the testing sample from Embodiment 16 was 0/0. The reaction index of the testing sample from Comparative Example 1 was 5/5.
- Cytotoxicity Test B
- This embodiment is a cytotoxicity test using MTT assay. Mouse fibroblast cells (CCRC 60091 NCTN Clone 929, of strain L) were implanted into each well of a 96-well plate and a minimum essential medium (MEM) containing 10% serum and 1% antibiotic was added to each well for cell culture. After the cells grew to a sub-confluent monolayer, 0.1 mL of test sample was added into part of the wells, and no other sample of the composite particles was added to the remaining wells do to act as a control group. Next, the 96-well plate was placed in an incubator with 5% carbon dioxide at 37° C. for 24 hours, and then MTT assay was conducted to analyze cell viability. One sample was investigated 3 times in total, and an average of the results was taken. In order to clearly describe the process of the testing, the product from Embodiment 8 will be used as an example to explain the preparation process. The product from Embodiment 16 and the product from Comparative Example 1 were also prepared for testing by the same process. 0.2 g of the product from Embodiment 8 was mixed with a minimum essential medium containing 10% serum and 1% antibiotic to form a solution with a 0.2 g/mL concentration. The cell viability of the testing sample from Embodiment 8 was 80.4±10.2%. The cell viability of the testing sample from Embodiment 16 was 99.4±8.6%. The cell viability of the testing sample from Comparative Example 1 was 35.4±4.9%.
- The results from Embodiments 18-19 are shown in Table 2. The test samples using the silicon dioxide composite particles from Embodiment 8 and Embodiment 16 were investigated, and the reaction index of cytotoxicity was RI=0/0. The cell viability assays were 80.4±10.2% and 99.4±8.6%, respectively. These results show that the sample was not cytotoxic. Accordingly, the silicon dioxide composite particles prepared from the precursor disclosed in the present disclosure does indeed have very low biotoxicity, which makes it of great potential for extensive use in organisms.
-
TABLE 2 Comparative silicon dioxide Embodiment Embodiment example composite particles 8 16 1 cytotoxicity none none Yes test A RI = 0/0 RI = 0/0 RI = 5/5 cytotoxicity none none Yes test B cell viability cell viability cell viability was 80.4 ± was 99.4 ± was 35.4 ± 10.2% 8.6% 4.9% - In summary, the organic silane precursor disclosed in the present disclosure can reduce the toxicity of silicon dioxide composite particles to organisms. Further, the long carbon chain of the organic silane precursor provides a steric barrier, which can prevent the alkoxysilane of the organic silane precursor from self-polymerization to form nano-particles and improve stability. Accordingly, the present disclosure provides the organic silane precursor, the method for preparing the silicon dioxide composite particles by using the organic silane precursor, and the silicon dioxide composite particles prepared from the organic silane precursor to solve the problems of conventional techniques and increase the applicability of the silicon dioxide composite particles.
- The above embodiments are given by way of illustration to help those skilled in the art to fully understand the spirit of the present application. Hence, it should be noted that the present application is not limited to the embodiments herein and can be realized by various forms. Further, the drawings are not a precise scale and components may be exaggerated in view of width, height, length, etc. Herein, the similar or identical reference numerals denote the similar or identical components throughout the drawings.
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